JP2003004935A - Color filter and method for manufacturing the same, liquid crystal element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease the number of processes and to reduce the influence of heat treatment on a coloring layer in a method for manufacturing a color filter having a transparent conductive film and spacers on the coloring layer. SOLUTION: The spacers are formed with a thermosetting resin composition. Heating and hardening treatment of the resin composition is performed to simultaneously attain annealing treatment of the transparent conductive film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter which is a constituent member of a color liquid crystal display used in a color television, a personal computer, a pachinko game table and the like, and a manufacturing method thereof, and further, to use the color filter. The liquid crystal device that was used.

[0002]

2. Description of the Related Art In recent years, liquid crystal displays have come to be used in various fields such as notebook personal computers and car navigation systems, taking advantage of their thinness, low weight and low power consumption.

Color filters used in color liquid crystal displays are manufactured by a pigment dispersion method on a transparent substrate such as glass.
By a dyeing method, an electrodeposition method, a printing method, an inkjet method or the like, a colored layer having a predetermined shape of the three primary colors of R (red), G (green) and B (blue) is formed, and the colored layer is further protected. For this purpose, a protective layer is formed, and then a transparent electrode for driving liquid crystal is formed on the protective layer.

At present, in a commonly used liquid crystal element, two glass substrates having electrodes are opposed to each other, and a liquid crystal is sandwiched between the two glass substrates. As spacers for keeping the distance between the two substrates constant, plastic beads or the like having a uniform particle diameter are scattered between the substrates.

Further, in an active matrix driving type color liquid crystal display, a switching element, for example, a TFT (thin film transistor) and a pixel electrode connected thereto, a TFT array in which a gate line and a source line for matrix wiring the TFT are formed. The substrate and the counter substrate on which the counter electrode and the color filter are formed are opposed to each other, and silver paste or the like as an electrode transfer material (transfer) is arranged in the peripheral portion of the screen, and the two substrates are electrically connected via the electrode transfer material. And the liquid crystal is sandwiched between the two substrates.

In these liquid crystal elements, the orientation of the liquid crystal around the spacers scattered between the substrates in order to make the distance between the two substrates uniform is disturbed, and light tends to leak from the peripheral portions of the spacers to lower the contrast. There is. Further, it is difficult to disperse the spacers uniformly, and if the spacers are non-uniformly arranged in the process of scattering the spacers on the substrate, display defects are caused and the yield of products is reduced. As measures against this, there has been proposed a method in which a spacer is formed in a columnar shape with a photoresist or the like at a position outside the display region, or a colored layer of a color filter is overlapped to form a spacer.

[0007]

The spacer using the above photoresist is usually formed on the color filter side substrate. That is, if necessary, a protective layer is formed on the colored layer of the color filter, a transparent conductive film to be an electrode is further formed, and an alignment film (alignment control film) is formed if necessary. Spacers are formed on a black matrix or a black stripe that shields adjacent colored pixels from light. In the case of manufacturing such a color filter with a spacer, at least the following steps are added as a step of the spacer in comparison with the manufacturing of the conventional color filter, which is a very large manufacturing load.・ The step of applying the photoresist solution on the transparent conductive film (or the alignment film) ・ The drying step of removing the solvent from the photoresist layer ・ The exposure step of irradiating the photoresist layer with ultraviolet rays through a mask ・ The ultraviolet rays of the photoresist layer Development process to dissolve and remove the unirradiated area ・ Heating process to heat the patterned photoresist layer

On the other hand, recently, there is an increasing demand for cost reduction of color filters, and it is inevitable to reduce the cost by totally simplifying the manufacturing process of the color filters.

Further, in order to secure the mechanical strength of the columnar spacer, it is an important requirement that the photoresist be cured by heat treatment. However, since the color layer of the color filter is made of an organic material, there is a concern that the color layer may change in color or peel due to an increase in the number of thermal processes.

On the other hand, in a liquid crystal element, an alignment film is often provided on a transparent conductive film, but such alignment film has uneven characteristics due to the unevenness of the surface of the transparent conductive film, resulting in a liquid crystal alignment state. May not be uniformly controlled. More specifically, a horizontal alignment film obtained by rubbing an organic film is widely used as the alignment film. However, when the surface of the organic film is not flat, the rubbing process is performed on the entire surface of the substrate in micron units. It becomes difficult to apply it uniformly. Such a problem is particularly remarkable when the thickness of the alignment film is thinner.

An object of the present invention is to provide a method of manufacturing a color filter in which the heat process for the colored layer is reduced, and the total number of steps is reduced to reduce the manufacturing load. And a transparent conductive film with high surface flatness,
Another object is to realize a color filter provided with a columnar spacer that has little influence on display, and to configure a liquid crystal element using the color filter.

[0012]

The first aspect of the present invention is to provide a light-shielding layer having a plurality of openings on a substrate, a colored layer having a plurality of colored portions of a plurality of colors for each color, and a transparent conductive film. A method of manufacturing a color filter having at least a columnar spacer formed in a region overlapping the light shielding layer, wherein a spacer pattern made of a thermosetting resin composition is formed on the transparent conductive film, and the spacer is formed. In the step of heating and curing the pattern to form the spacer, the annealing treatment of the transparent conductive film is simultaneously performed by performing the heat curing treatment of the spacer pattern at a temperature higher than the film forming temperature of the transparent conductive film. A method of manufacturing a color filter, which is characterized in that

In the method for manufacturing a color filter of the present invention, the following constitution is included as a preferable aspect. The substrate temperature during film formation of the transparent conductive film is 150 ° C. or lower.
The heat curing temperature of the spacer pattern is 180 to 250.
℃. The thermosetting resin composition has photosensitivity, and the thermosetting resin composition layer is subjected to pattern exposure and development to form a spacer pattern. In the step of forming the thermosetting resin composition layer, after forming a coating film of the thermosetting resin composition, the coating film is heated and dried at 60 to 150 ° C. The thermosetting resin composition is photosensitive, and the step of forming the spacer pattern includes a drying treatment at 60 to 150 ° C. The heat curing treatment of the spacer pattern is performed with a hot plate. The transparent conductive film is made of a transparent conductive material containing In ₂ O ₃ as a main component. The colored layer is formed by an inkjet method.

In a second aspect of the present invention, a light shielding layer having a plurality of openings on a substrate, a colored layer having a plurality of colored portions of a plurality of colors for each color, a transparent conductive film, and the light shielding layer are overlapped. A color filter having at least a columnar spacer formed in a region, wherein the transparent conductive film has a specific resistance of 2.5 × 1.
The color filter has a value of 0 ⁻⁴ Ωcm or less and is manufactured by the color filter manufacturing method of the present invention.

In the color filter of the present invention,
It is preferable to have a protective layer between the colored layer and the transparent conductive film.

Further, a third aspect of the present invention is a liquid crystal device characterized in that a liquid crystal is sandwiched between a pair of substrates, and one of the substrates is constructed by using the color filter of the present invention. .

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a color filter of the present invention, the heat curing treatment of the resin composition in the step of forming the spacer using the thermosetting resin composition also serves as the annealing treatment of the transparent conductive film. It is characterized by Therefore, it is possible to reduce the total number of steps and reduce the cost of the color filter. Furthermore, by appropriately setting the heat curing temperature in the heat curing treatment, the substrate temperature at the time of forming the transparent conductive film, and the heat drying temperature of the thermosetting resin composition layer, the specific resistance of the transparent conductive film and the surface flatness can be improved. It is possible to control the properties, transparency, and stress, and at the same time prevent deterioration of the colored layer due to a thermal process. Hereinafter, the color filter and the manufacturing method of the present invention will be described with reference to embodiments.

The color filter of the present invention has, as a basic configuration, a light-shielding layer having a plurality of openings on a substrate, a colored layer having a plurality of colored portions of a plurality of colors for each color, and a transparent conductive film.
A columnar spacer is formed in a region overlapping the light shielding layer, and a protective layer is provided between the colored layer and the transparent conductive film, if necessary.

In the present invention, as a method for forming a colored layer, a conventional color filter manufacturing method, that is, the above-mentioned dyeing method, pigment dispersion method, printing method or the like can be used, but in particular, the surface unevenness is small. An inkjet method capable of forming a flat colored layer is preferably used.

FIG. 1 and FIG. 2 schematically show the steps of a preferred embodiment of the manufacturing method of the present invention in which the colored layer is formed by an ink jet method. In the figure, 1 is a support substrate, 2
Is a black matrix, 3 is an ink receiving layer, 4 is a photomask, 5 is a non-colored portion, 6 is a colored portion, 7 is ink, 9 is
Is a colored portion, 10 is a protective layer, 21 is a transparent conductive film, 22 is a thermosetting resin composition layer, 23 is a photomask, and 24 is a spacer.

The relationship between the spacers 24 of the color filter of the present invention and the black matrix 2 obtained by the steps of FIGS. 1 and 2 is schematically shown in FIG. 3 in a plan view. still,
The process of FIG. 1 corresponds to the AA ′ cross section of FIG. 3, and the process of FIG. 2 corresponds to the BB ′ cross section of FIG. Hereinafter, each step will be described in detail with reference to FIGS. 1 and 2, and FIGS. 1 (a) to 1 (d) and FIG.
Each step of (e) to (g) is a schematic sectional view corresponding to each step of the following steps (a) to (g).

Step (a) A light-shielding layer having a plurality of openings and then an ink receiving layer 3 are formed on the supporting substrate 1. This embodiment is an example in which the black matrix 2 is formed as the light shielding layer, and the light shielding layer may be a black stripe.

As the supporting substrate 1 used in the present invention,
Generally, a glass substrate is used, but the substrate is not limited to the glass substrate as long as it has necessary properties such as transparency and mechanical strength as a color filter, and a plastic substrate or the like can be used. The black matrix 2 is usually a Cr metal film or Cr-Cr.
Although a laminated film of O _x is used, a so-called resin black matrix in which a black pigment such as carbon black is dispersed in a resin may be used if necessary.

The ink receiving layer 3 is a coloring medium for forming the colored portion 9 by coloring in the step described later, and is preferably a photosensitive resin composition whose ink receiving ability is changed by light irradiation or light irradiation and heat treatment. Then, in the next step, pattern exposure is performed to form the non-colored portion 5 for preventing color mixture. The photosensitivity may be either negative type or positive type, and specifically, acrylic resin, epoxy resin, silicone resin, hydroxypropyl cellulose,
Cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose or modified products thereof, amide resins, phenol resins, polystyrene resins and the like are used in combination with a photoinitiator (crosslinking agent) as required. As the photoinitiator, dichromate,
Bisazide compounds, radical initiators, cationic initiators, anionic initiators, etc. can be used.
These photoinitiators can be used as a mixture or in combination with other sensitizers. Furthermore, it is also possible to use a photoacid generator such as an onium salt as a crosslinking agent. The present embodiment shows an example using a negative resin composition that loses (or reduces) the ink receiving ability by light irradiation.

The above-mentioned photosensitive resin composition is spin coated,
It is applied on the transparent substrate 1 by a method such as roll coating, bar coating, spray coating, or dip coating, and if necessary, prebaked to form the ink receiving layer 3. The thickness of the ink receiving layer 3 is usually about 0.3 to 3.0 μm.

Step (b) When the ink receiving layer 3 is formed of a photosensitive resin composition, the ink receiving layer 3 is pattern-exposed using the photomask 4 to eliminate the ink receiving ability of the exposed portion (or At least, the non-colored portion 5 is formed. The area that has not been exposed in this step becomes the colored portion 6. Non-colored part 5
Is formed at a position overlapping the black matrix 2, and in particular, from the viewpoint of preventing white voids at the opening boundary of the black matrix 2, it is preferable that the non-colored portion 5 be narrower than the width of the black matrix 2. .
Further, since the colored pixels of the same color (the colored portion regions in the openings of the black matrix 2) are arranged in the scanning direction of the inkjet head, the opening rows of the black matrix 2 arranged in dots along the scanning direction. Against
By forming the non-colored portions 5 in a stripe shape parallel to each other across the opening row, stripe-shaped colored portions 6 parallel to the scanning direction are formed, and the ink 7 is continuously applied to the colored portions 6 during coloring. It is preferable because it can be discharged.

Further, in order to enhance the effect of preventing color mixture, it is also preferably applied to the ink receiving layer 3 that the non-colored portion 5 develops ink repellency. When a positive resin composition that exhibits (or increases) the ink receiving ability by exposure is used, the exposure may be performed in the reverse pattern.

Step (c) An ink-jet head (not shown) ejects ink 7 of a predetermined color onto the portion 6 to be colored along a predetermined coloring pattern for coloring.

The ink jet method used in the present invention is a bubble jet (registered trademark) type using an electrothermal converter as an energy generating element, or
A piezo jet type using a piezoelectric element or the like can be used, and the coloring area and coloring pattern can be set arbitrarily.

The ink 7 used for coloring the ink receiving layer 3 is preferably any ink as long as it contains a coloring agent such as a dye or a pigment and is liquid at the time of ejection.

Step (d) A necessary treatment such as heat treatment or light irradiation is carried out to cure the entire ink receiving layer to form a colored layer consisting of the non-colored portion 5 and the colored portion 9.

Further, if necessary, a protective layer 1 may be provided on the colored layer.
Form 0. As the protective layer 10, a photocurable type, a thermosetting type, or a combination of heat and light curing type resin composition layer, or an inorganic film formed by vapor deposition, sputtering or the like can be used. In any case, any material can be used as long as it has transparency as a color filter and can withstand the subsequent transparent conductive film forming step, alignment film forming step and the like.

Step (e) A transparent conductive film 21 is formed on the colored layer or the protective layer 10, and a thermosetting resin composition layer 22 as a spacer forming material is further formed thereon.

In the present invention, as the transparent conductive material forming the transparent conductive film 21, indium tin oxide (IT
O), zinc oxide, tin oxide, and alloys thereof can be used. In particular, a transparent conductive material mainly composed of In ₂ O ₃ is preferable because it is chemically stable, has a low resistance value, high transparency, and does not impair the color display characteristics. The thickness of such a transparent conductive film 21 is usually 0.01 to
It is 1 μm, preferably 0.03 to 0.5 μm. In the present invention, the substrate temperature during film formation of the transparent conductive film 21 is set to 1
It is desirable to set the temperature to 50 ° C. or lower, which is lower than the crystallization temperature of the transparent conductive material. More preferably, by forming the film at 100 ° C. or lower, leaf-shaped grains are not formed, so that the transparent conductive film 21 having a very smooth surface can be obtained.
Even when the stress of the transparent conductive film 21 is low and the annealing temperature of the transparent conductive film 21 described later is increased by forming the film at a low temperature, the transparent conductive film 21 and the colored layer or the protective layer 10 are Wrinkles and cracks due to the difference in linear expansion coefficient between the two are prevented.

The thermosetting resin composition used in the present invention is preferably photosensitive and a commercially available ultraviolet curable resist can be preferably used.
The present embodiment is an example using such a resist, and is applied over the entire surface of the transparent conductive film 21 in a thickness range of 1 to 10 μm. As a coating method, a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, or the like is preferably used, and thereafter, it is dried by heating using an oven or a hot plate.

With the thermosetting resin composition layer 22 formed, the transparent conductive film 21 is sandwiched between the resin layers and is not completely crystallized, so that many crystallographic defects are present inside. contains. In this state, when the thermosetting resin composition layer 22 is heated and dried at a temperature higher than the film formation temperature of the transparent conductive film 21 and lower than the crystallization temperature for a long time, the resin layer is removed from the resin layer. In contamination due to degassing or diffusion of oxygen and oxygen depletion existing between crystal lattices in the transparent conductive film 21 to the surface, in an annealing treatment which also serves as a heat curing treatment step, which will be described later,
This has the effects of increasing the annealing time, preventing the specific resistance of the transparent conductive film 21 from decreasing, and decreasing the transparency.

FIG. 5 shows the transparent conductive film 21 (IT) depending on the heating time in the annealing treatment when the heating and drying temperature of the thermosetting resin composition layer 22 is changed from 60 ° C. to 180 ° C.
The state of the decrease in the specific resistance of O) is shown. As shown in FIG.
When the drying temperature is 60 ° C. to 120 ° C., the crystallization of the transparent conductive film 21 progresses rapidly and the specific resistance is lowered in about 3 minutes, whereas when the drying temperature is 160 ° C., the same 3 minutes is required. The annealing treatment does not reduce the resistivity to the same level as 60 ° C to 120 ° C. Practically, the specific resistance is 2.5 × 10 ^-4 Ωc
If it is m or less, there is no problem. Therefore, the drying condition of the thermosetting resin composition layer 22 varies depending on the resin used, the solvent, and the coating amount, but it is preferably 1 to 30 minutes at 60 to 150 ° C. More preferably, in order to simplify the process, the temperature is set to 60 ° C. to 100 ° C. for about 1 to 10 minutes.

Step (f) When the thermosetting resin composition layer 22 is photosensitive, a position overlapping the black matrix 2 via a photomask 23 having an opening at a position for forming a spacer (this embodiment). Then, light is applied to the intersection of the black matrix 2). When the thermosetting resin composition is an ultraviolet curable resin, the wavelength of the ultraviolet ray used is set according to the sensitivity of the resin composition, but is generally 365 nm. Then, after developing with an alkaline developer, a columnar spacer pattern is formed. In the present invention, the shape of the pattern may be either a cylinder or a quadratic prism, and may be a cone or a pyramid.

Step (g) The columnar spacer pattern is subjected to a predetermined heat curing treatment (post-baking) to be cured, thereby forming the columnar spacer 24. In the present invention, the heat curing treatment also serves as the annealing treatment of the transparent conductive film 21, and the transparent conductive film 21 is crystallized by the treatment to have a low specific resistance and high transparency.

In the present invention, when the heat curing temperature in the main heat curing treatment is low, the specific resistance and transparency of the transparent conductive film 21 are not improved, and the brightness when a liquid crystal element is constructed by using the color filter. Results in problems such as low. Further, the mechanical strength such as hardness and adhesion of the columnar spacer 24 becomes insufficient, so that the spacer 24 is likely to be peeled off or deformed. As a result, there arises a problem that the reliability of the liquid crystal element is lowered.

On the other hand, if the heat curing temperature is too high,
This may cause deterioration of the colored layer. FIG. 6 shows the specific resistance of the transparent conductive film 21 (ITO) depending on the heat curing temperature.
FIG. 7 shows the color difference ΔE ^* _ab before and after the heat curing treatment of each of the R, G, and B colored portions 9.

As is apparent from FIG. 7, the heating temperature is 25
At 0 ° C. or higher, the colored portion of B has ΔE ^* _ab of 3 or more, which is not preferable. In addition, G reaches ΔE ^* _ab above 230 ° C.
Will be 3 or more. As described above, since the colored layer is formed of an organic material, there is a limit to heat resistance, and heating at 230 ° C. or higher causes deterioration not a little, though it varies depending on the type of organic material used. Conventionally, since the heat treatment of the transparent conductive film 21 and the heat curing treatment of the spacer pattern are performed twice, the damage to the colored layer is large. On the other hand, in the present invention, since the heat treatment is performed only once, the damage of the coloring layer is significantly reduced, but as described above, when the heating temperature is too high, the deterioration of the coloring layer cannot be avoided. . Further, when the treatment is performed at a high temperature, there is a problem that wrinkles and cracks occur due to the difference in linear expansion coefficient between the transparent conductive film 21 and the colored layer or the protective layer 10. If 21 is formed at a low temperature, the stress of the transparent conductive film 21 is low, so that generation of wrinkles and cracks is prevented. Therefore, in the present invention, the heat curing temperature in the annealing treatment of the transparent conductive film 21 which also serves as the heat curing treatment for the spacer pattern is preferably 180 to 250 ° C, more preferably 190 ° C to 230 ° C.

As the method of the heat curing treatment, hot plate heating, oven heating, etc. are generally used, but it is preferable to use the hot plate from the viewpoint of lead time and particles.

FIG. 8 shows the difference in the temperature rising characteristics of the substrate between the hot plate and the oven. In the figure, the solid line indicates the hot plate and the broken line indicates the oven. As shown in FIG. 8, in the hot plate, the substrate temperature rises sharply and the time to reach the target temperature is shorter than in the case where an oven is used. This not only reduces the processing time but also affects the annealing process of the transparent conductive film. That is, in the annealing treatment of the transparent conductive film, it is easier to crystallize when a high temperature is applied for a short time, and the difference between the optimum oxygen partial pressure conditions at the time of film formation at the time of film formation becomes small. Control of the oxygen flow rate becomes easy. Therefore, in the present invention, it is desirable to perform heat curing treatment using a hot plate.

As a heating method using a hot plate, there are a contact type and a proxy type. However, even with a proxy, it is possible to heat rapidly by bringing the substrate as close as possible to the hot plate. In the present invention, either method can be preferably used.

FIG. 4 shows a schematic cross-sectional view of one embodiment of a liquid crystal element constituted by using the color filter obtained in the steps of FIGS. In the figure, reference numeral 41 is a counter substrate, 42 is a pixel electrode, 43 and 44 are alignment films, and 45 is a liquid crystal. The same members as those in FIGS.
Incidentally, FIG. 4 is a sectional view at a position corresponding to AA ′ in FIG.

In the color liquid crystal element, generally, the substrate 1 on the color filter side and the counter substrate 41 are put together to form a liquid crystal 45.
Is formed by encapsulating. TFTs (not shown) and pixel electrodes 42 are formed in a matrix on the inside of one substrate 41 of the liquid crystal element. Further, inside the substrate 1 on the color filter side, at a position facing the pixel electrode 42,
The colored portion 9 of the color filter is formed so that R, G, and B are arranged, and the transparent conductive film 21 is formed thereon.
Further, alignment films 43 and 44 are formed on the surfaces of both substrates, and liquid crystal molecules are arranged in a fixed direction. These substrates are arranged to face each other with a predetermined distance by the spacer 24 of FIG. 2, are bonded by a sealing material (not shown), and the liquid crystal 45 is filled in the gap.

In the case of a transmissive liquid crystal device, the substrate 41 and the pixel electrode 42 are formed of a transparent material, a polarizing plate is adhered to the outside of each substrate, and generally a fluorescent lamp and a scattering plate are combined. The display is performed by using a backlight and causing the liquid crystal compound to function as an optical shutter that changes the light transmittance of the backlight. In the case of a reflective type, the substrate 41 or the pixel electrode 42 is formed of a material having a reflection function, or a reflective layer is provided on the substrate 41 and a polarizing plate is provided outside the transparent substrate 1, The display is performed by reflecting the light incident from the filter side.

Further, in the liquid crystal element of the present invention, it goes without saying that, as long as it is configured using the color filter of the present invention, conventional techniques can be used as it is for other members.

[0050]

Example [Formation of Colored Layer] On a glass substrate having a black matrix formed thereon, a resin composition having the following composition was dissolved in ethyl cellosolve and spin-coated so as to have a film thickness of 2 μm, and then at 90 ° C. Prebaking was performed for 20 minutes to form a resin composition layer (ink receiving layer).

[0051] ・ Composition of resin composition   Acrylic copolymer 97 parts by weight   Methyl methacrylate 50 parts by weight   Hydroxyethyl methacrylate 30 parts by weight   N-methylol acrylamide 20 parts by weight   Triphenylsulfonium hexafluoroantimonate 3 parts by weight

Next, the resin composition layer on the black matrix is pattern-wise exposed in a stripe pattern through a photomask having a stripe-shaped opening narrower than the width of the black matrix, and further on a hot plate at 120 ° C. Heat treatment was performed for 1 minute. Then, for the unexposed portion, R, G, B are used by using an inkjet recording device.
Dye ink is applied and the stripe pattern is colored with continuous dots, then the ink is dried at 90 ° C. for 5 minutes, and then heat treated at 200 ° C. for 60 minutes to cure the resin composition layer, A colored layer was formed.

Then, a two-component thermosetting resin composition ("Optomer SS66" manufactured by Japan Synthetic Rubber Co., Ltd. was formed on the colored layer.
99G ") is spin-coated to a film thickness of 1 μm,
After prebaking at 90 ° C. for 30 minutes, heat treatment was performed at 230 ° C. for 60 minutes to form a protective layer.

[Film Formation of Transparent Conductive Film] A transparent conductive film was formed on the protective layer by sputtering. A Fe-Ni alloy (42 alloy) material was used for the mask that limits the film formation region, the thickness of the mask was 0.2 mm, and the opening shape of the mask was formed by etching by photolithography. For positioning with respect to the substrate, cover the glass substrate with the mask,
On the dedicated stage, the two sides, which are the reference surfaces of both the glass substrate and the mask, were abutted against the reference pins provided on the dedicated stage. Then, the mask and the substrate were temporarily fixed by using a clip-shaped jig.

The substrate on which the mask is fixed as described above is put into the single-wafer sputtering apparatus from the external cassette, heated to the film forming temperature shown in Table 1 in the heating chamber, and then transferred to the sputtering chamber to obtain a transparent conductive film. A film was formed. At that time, heating was performed from the back surface so that the substrate was kept at a predetermined film forming temperature even in the sputtering chamber. The sputtering target is I
A sintered compact target containing 10 wt% SnO ₂ in n ₂ O ₃ and having a purity of 99.99% and a relative density of 98% or more was used. Also, 5 × 10 ^-5 by cryopump
Ar flow rate: 180 scc when exhausted below Pa
m, O ₂ flow rate: 2.5 sccm, sputtering pressure:
The ITO film was formed at 0.6 Pa. During film formation, the cathode magnet placed behind the target was swung to control the film thickness to be uniform in the plane. The power applied to the cathode is 2.3 kW,
The film was formed to have a film thickness of 135 nm.

In the film forming chamber, an Sm-Co magnet is arranged in the heat equalizing plate in conformity with the shape of the mask so that the mask is more closely attached to the substrate, and the substrate is sandwiched by the magnet. The film was formed in the shape. The substrate on which the film formation was completed was collected in a dedicated cassette in the loading / unloading chamber, then opened to the atmosphere, and taken out to an external cassette. Then, the mask fixed by the jig was removed, and the film formation was completed.

In Table 1, No. For Nos. 7 and 8, after the transparent conductive film was formed, the same annealing treatment as the conventional one was performed for 8 minutes before the spacer formation.

[Formation of Spacer] A spacer material (“Optomer NN-700” manufactured by Japan Synthetic Rubber Co., Ltd.) containing no pigment is applied on the entire surface of the substrate on which the transparent conductive film is formed in the above step by a spinner and then hot. The plate was heated and dried at the temperature shown in Table 1 for 5 minutes. Next, ultraviolet rays having a wavelength of 365 nm are irradiated through a photomask having an opening at a desired position on a black matrix where a spacer is to be formed, development is performed for 60 seconds with an alkaline aqueous solution, and the temperature is shown in Table 1 on a hot plate. Was heat-cured for 8 minutes to form spacers.

[Evaluation] Specific resistance of the transparent conductive film: Calculated from the surface resistance measured by the four-point probe method. Color difference ΔE ^* _ab of the colored portion between the steps after the formation of the protective film and the spacer: The spectral transmittance of each of the colored portions of R, G and B was previously measured by the Olympus “OSP-2000” after the formation of the protective film.
In the visible region of wavelength 400-700 nm,
It was measured in a reference with 100% glass. Thereafter, after the spacer is formed, similarly, for the same colored portion, the region on the transparent conductive film where the colored portion does not exist is 100 times.
%, And the color difference ΔE ^* _ab in the L ^* _ab color system was measured for each colored part before and after the formation of the transparent conductive film and the spacer. ΔE ^*
It is said that the color difference cannot be discriminated by human eyes when _ab is 3.0 or less.

Durability test: After immersing the color filter in boiling water for 1 hour, it was observed with a microscope to confirm whether or not cracks were generated on the surface of the transparent conductive film. After leaving each color filter for 12 hours in a chamber kept at a temperature of 125 ° C and a humidity of 85%, 250 ° C
After heating for 5 minutes on the hot plate of No. 3, the wrinkle state was observed by a differential interference microscope. The results are as follows: A: not confirmed at all, B: surface is slightly changed into particles, C:
It was classified into three stages: wrinkle occurrence.

Surface flatness: The surface of the colored portion of the color filter was observed with a SEM (scanning electron microscope) at a magnification of 35,000. When leaf-shaped grains were observed on the surface, "x" was observed, and when not observed, the surface was smooth and regarded as good, and evaluated as "○".

Table 1 shows conditions and results for manufacturing the color filter.

[0063]

[Table 1]

No. shown in Table 1 When the heights of the 100 color spacers from the transparent conductive film were measured for the color filters 1 to 6, the average height was 4.0 μm and the variation was 1.0 μm or less. In addition, No. 11-13
When the height of the spacer was similarly measured for the color filter of No. 1, the average height was 4.2 μm and the variation was 1.
It was 8 μm.

[0065]

As described above, according to the present invention,
Compared to the conventional color filter manufacturing method that forms a spacer using a resist, the number of steps is reduced,
Manufacturing costs are reduced.

Further, the film forming temperature of the transparent conductive film, the heat drying temperature of the thermosetting resin composition layer in the spacer forming step,
By setting the heat-curing temperature appropriately, it suppresses the influence on the colored layer and at the same time enhances the annealing treatment effect of the transparent conductive film, has good transparency and low specific resistance, and has a flat surface with no wrinkles or cracks. A color filter including a conductive film and a colored layer that is not deteriorated by heat treatment is obtained,
By using the color filter, a liquid crystal element having high reliability and excellent color display characteristics can be provided at a lower cost.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a step of a preferred embodiment of a method for manufacturing a color filter of the present invention.

FIG. 2 is a schematic sectional view showing a step of a preferred embodiment of the method for manufacturing a color filter of the present invention.

FIG. 3 is a schematic plan view showing a relationship between a black matrix and a spacer of an embodiment of a color filter of the present invention.

FIG. 4 is a schematic sectional view of an embodiment of a liquid crystal element of the present invention.

FIG. 5 is a diagram showing the heating and drying temperature dependency of the specific resistance of the transparent conductive film in the spacer forming step.

FIG. 6 is a diagram showing the temperature dependence of the specific resistance of the transparent conductive film on the heat curing treatment temperature of the spacer pattern in the spacer forming step.

FIG. 7 is a diagram showing the heat curing treatment temperature dependency of the color difference of each colored portion before and after the heat curing treatment of the spacer pattern in the spacer forming step.

FIG. 8 is a diagram showing a difference in temperature rising characteristics of a substrate between a hot plate and an oven.

[Explanation of symbols]

1 Support substrate 2 Black matrix 3 Ink receiving layer 4 photo mask 5 Non-colored part 6 Colored part 7 ink 9 Coloring part 10 Protective layer 21 Transparent conductive film 22 Thermosetting Resin Composition Layer 23 Photomask 24 spacer 41 Counter substrate 42 pixel electrode 43,44 Alignment film 45 LCD

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G09F 9/30 320 G09F 9/30 320 349 349B 349C 9/35 9/35 F term (reference) 2H048 BA11 BA64 BB01 BB08 BB37 BB44 2H089 LA07 LA09 QA12 QA16 TA01 TA09 TA12 2H091 FA02Y FA35Y GA01 GA13 LA12 LA30 5C094 AA43 AA44 AA45 BA43 CA19 CA24 EA04 EA05 EA07 EC03 ED03 ED15 5G435 AA12 KK05 CC09 CC09 KK13 CC12 CCBB

Claims (11)

[Claims] 1. A light-shielding layer having a plurality of openings on a substrate, a colored layer having a plurality of colored portions of a plurality of colors for each color, a transparent conductive film, and a region formed in a region overlapping the light-shielding layer. A columnar spacer, and a spacer pattern made of a thermosetting resin composition is formed on the transparent conductive film, and the spacer pattern is heated to cure the spacer pattern. In the step of forming a film, a method for manufacturing a color filter, characterized in that the transparent conductive film is annealed at the same time by performing a heat curing process on the spacer pattern at a temperature higher than the film forming temperature of the transparent conductive film. . 2. The substrate temperature during the formation of the transparent conductive film is 1
The method for producing a color filter according to claim 1, which is 50 ° C. or lower. 3. The method of manufacturing a color filter according to claim 1, wherein the heat curing temperature of the spacer pattern is 180 to 250 ° C. 4. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition has photosensitivity, and the thermosetting resin composition layer is subjected to pattern exposure and development to form a spacer pattern. Color filter manufacturing method. 5. The method according to claim 4, wherein in the step of forming the thermosetting resin composition layer, after forming a coating film of the thermosetting resin composition, the coating film is dried by heating at 60 to 150 ° C. Color filter manufacturing method. 6. The method of manufacturing a color filter according to claim 1, wherein the heat curing treatment of the spacer pattern is performed with a hot plate. 7. The method for producing a color filter according to claim 1, wherein the transparent conductive film is made of a transparent conductive material containing In ₂ O ₃ as a main component. 8. The method for manufacturing a color filter according to claim 1, wherein the colored layer is formed by an inkjet method. 9. A light shielding layer having a plurality of openings on a substrate, a colored layer having a plurality of colored portions of a plurality of colors for each color, a transparent conductive film, and a region formed in a region overlapping the light shielding layer. 9. A method of manufacturing a color filter according to claim 1, wherein the transparent conductive film has a specific resistance of 2.5 × 10 ⁻⁴ Ωcm or less. A color filter manufactured by. 10. The color filter according to claim 9, further comprising a protective layer between the colored layer and the transparent conductive film. 11. A liquid crystal is sandwiched between a pair of substrates,
A liquid crystal device, wherein one of the substrates is formed by using the color filter according to claim 9.